Amide condensation products



United States Patent 2,813,091 AMIDE CONDENSATION PRODUCTS John D. Zech,Wilmington, Del., assignor to Atlas Powder Company, Wilmington, Del., acorporation of Delaware No Drawing. Application May 4, 1953,

Serial No. 353,005 1 7 Claims. (Cl. 260211) The present inventionrelates to condensation products formed by the interaction of asecondary hexityl amine, formaldehyde and an amide, and to a process formaking the same.

In copending application Ser. No. 337,691, filed February l8, 1953,there are disclosed condensation products of hexityl amines withformaldehyde, a phenol and certain polyamides, particularly urea andmelamine. This application, which is continuation-in-part of the saidcopending application, is directed to condensation products of amides ingeneral with formaldehyde and hexityl amines.

It is an object of the invention to provide the named condensationproducts as new composition.

Another object is to provide a process for making the condensationproducts.

A specific object is to provide condensation products of N-methylglucamine, formaldehyde and amides.

The above and other objects will become apparent in the course of thefollowing description.

The products of the invention have novelproperties making them suitablefor a variety of uses. By reason of their reactive groups they areuseful as chemical intermediates. Particular compounds of the class areuseful as surface active agents, anti-static agents, textile finishingand processing assistants, corrosion inhibitors, lubricant additives,waxes, or synthetic resins.

The term hexityl amines is used herein to define compounds from thegroup having the structure of hexitols with one hydroxyl group replacedby an amino group. They are the reduction products of hexosamines andare preferably made by the simultaneous reaction of ammonia, or aprimary amine, and hydrogen on a hexose by methods well known to theart. Secondary hexityl amines result when the nitrogen containingcompound entering the reaction is a primary amine. Among such secondaryhexityl amines may be named N-meth-yl glucamine, N- methyl fructamine,N-ethyl, N-butyl, N-benzyl, N-phe'nyl, N-cetyl, etc., glucamines, orN-propyl, N-allyl, N-oleyl, N-tolyl, etc., fructamines. W I

The compounds of the invention are condensation products of secondaryhexityl amines with formaldehyde and amides. .Amides, suitable forpreparation of the novel condensation products, contain at least onereactive amido hydrogen and may be mono-, dior polyamides. They may bederived from carboxylic acids or sulfonic acids. An exemplifying, butnon-limiting, list of amides which may be condensed with secondaryhexityl amines and formaldehyde in accordance with the invention is asfollows: i

Oxalic diamide Myristic amide Behenrc am1de Palmitic amide Sebacicdiamide Dilinoleic acid. diamide Erucic amide Linoleic amide Benzenesulfonamide When the condensing amide is a monoamide, the prod ucts ofthe invention are those resulting from the reaction of equimolarproportions of secondary hexityl amine, formaldehyde, and amide. Theproduct, then, contains the amido radical linked through methylene tothe second ary hexityl amino radical. Condensation products from diandpolyamides are those obtained by employing, per mol of polyamide, fromone to n mols of formaldehyde and from 1 to n mols of secondary hexitylamine, where n is the number of amido radicals per mol of polyamide. Theproducts thus contain one or more hexityl amino radicals linked throughmethylene groups to polyamido residues which may or may not contain freemethylol groups and unreacted amido radicals.

In preparing the condensation products the formaldehyde may beintroduced into the reaction mixture in the form of aqueous or alcoholicsolutions, or in the form of a. polymer such as a paraformaldehyde.

The condensation may be carried out in a single stage or stepwise. Mostsimply the amine, amide, and formaldehyde are dissolved in a suitablesolvent, such, for example, as water or alcohol, refluxed for severalhours and recovered from the solvent by distilling off the latter.Alternatively, the amide may be first reacted with formaldehyde to forma methylol amide, which then may be further condensed with a hexitylamine. The stepwise procedure is especially satisfactory when apolyamide is being condensed with fewer mols of hexityl amine than thenumber of amide radicals. The following examples illustrate thepreparation of specific condensation products in accordance with theinvention.

Example 1 493 grams of N-methyl glucamine and 505 grams of a commerciallauric amide (Armours Armid 12) were dissolved in 1750 ml. of methanol,and grams of paraf ormaldehyde added. The mixture was heated for twohours under a reflux condenser, after which time the methanol and waterof reaction were removed by distillation. Distillation was conducted atfirst: under atmosphere pressure and finally under high vacuum (1 to 2millimeters of mercury) at a maximum temperature of to C. Thecondensation product remaining in the pot was a firm waxy product ofpronounced surface activity- Example 2 Example 3 199 grams of N-methylglucamine, 281 grams of commercial oleic amide and 30 grams ofparaformaldehyde were dissolved in 1030 ml. of methanol. The mixture washeated to boiling and refluxed for two hours. Solvent was removed as inthe preceding examples. The still residue was a soft wax comprising theradicals of N methyl 'glucamine and oleic amide, linked by theirrespective nitrogen atoms through a methylene bridge.

Example 4 A resinous Condensation product was o b t"n' ed y refluxingtogether for 1.5 hours a solution o f 0.5 grams of urea, 200 grams ofNunethyl glucamine and grams of 37% formalin in. 100 ml. of water. Ther'esin was recovered from the solution by distilling oiT the water undervacuum.

Example A resinous condensation product was prepared from melamine,formaldehyde, and N-methyl glucamine as follows: 68.5 grams of melamine,33 grams'ofparaformalde hydeand 212 grams of N-methyl-glucamine, alldissolved in- 200 ml. of water were heated to boiling in a reactionfiask and held at a temperature offrom-8010 103? C. under-refluxconditions. After 2% hours reaction time, cc.-of 37% aqueousformaldehyde was added and heating continued. After 4% hours reactiontime a second portion of 20 cc. of 37% formaldehyde solution wasadded..=--After 5 /3 hours reaction time the w ater was distilled fromthe solution and the product cooled to a brittle glassy resin. Per molof melamine, there was-employed 2-mols of N-methyl glucamine and 3 molsof formaldehyde. 1

Example 6 A highly hydrophilic condensation product was prepared byrefluxing together for one hour a't 90 to 103 1, 118 grams of acetamide,390 grarns of N -methyl 'fglucamine, and 170 grams of 37% aqueousformaldehyde solution, all diluted with 60 ml. ofv water. From.thereaction mixture 105 ml. of water was distilled'olf, leaving aviscous syrup of 84% solids content comprising N- methyl,N-acetamidomethyl glucamine.

Example 7 for 36'minutes the following ingredients: grams urea 22.5mm pq t ials ehrdey 97.5 grams N-methyl glucamine 00. 21- W er, .7

The cooled solution possessed no odor of formaldehyde, showing that thereaction had gone to completion.

Example 9 24.3 grams of N-methyl glucamine, 1"8.3" .g 1 'a rns ofphthalimide, and 3.75 grams ofparaformaldehyde, all dissolved in 150 ml.of methanol were refluxed for 72 minutes at 66 to 69 C. s The methanolwas distilled off to yield a resinous product which was NphthalirnidomethyLN-methyl glucamine. I I I I Properties of condensationproducts made inf-accordance with the invention may vary over afwiderangefdepending upon the choice of amine and'amide. In the absence ofany radical ofsubstantial hydrocarbon content (the products of Examples6,;7, and 8,. forexample), the products are water-soluble and'hydrophilic jThey may be employed as hygroscopic conditionin'g lagentsin glue formulations, in paper or cellophane, and, the, like, orcausedto reactwith polybasic acids, such asboricl acid, to yield resinous filmformers.

The introduction of one or more high molecular weight hydrocarbonradicals into the compound; as by employing N-cetyl glucamine, orstearic amide, or both in the condensation, increases the hydrophobiccharacter thereof and decreases the water solubility. The condensatescontaining both the hydrophilic glucamine residues and hydrophobicradicals are strongly surface active.

The cond sa on pr du t .pi. :the. xeptiqn contain functional groupswhich ar chemically reactive. They v the r t at s iflie nth derivatives.The hydroxyl radicals of 'the 'glucamineresidue may be esterified withorganic or inorganic acid, etherified to replace the hydroxylgroups,with. alkoxy groups, aryloxy groups, and "the like, oncondensed withalkylene oxides to yield hydroxyalkylethers or polyglycol ethers. Thetertiary nitrogeh' atornsof the condensates are susceptible ofquaternization in the usual manner and, when so treated, the condensatesexhibit strong, cationic surface rit 7.

Polyamides, condensed with. hexityl amines in a ance with theinventiomtendto yield resinous centre tion products, particularly ifmorethan one mol of formaldehyde ise'mployedper amido radical.

'The following example illustrates, the condensatio enemies ether than acarboxylic amide in aces-wanes with v hei riihelttican. I I II "Example10 I I 815. 5 grams of p -toluene sul fonamide, 9 7.5I g rfams of methylglu cam'ine, 15 grams of parafo'rmaldehyde and 350cc. ofmethanolwereheated together at reflux tempasture for hours after whichtheinethanol was distilled Qifusing vacuum 'att'he end. The maximumtemperature 'reaehe'd was 114 C. The residuearnounting, to.1 88 gramswasa light amber c olored viscous liguid while hot Aftercoolingf to.room tem perature it was a soft. tatfy -jlikenmaterial whichfcrystallized slowly. II

From the several detailed examples given, these slgilled in: the. artwill readilytp'erceive .to prepar e analog ous condensation'produetsfrom formaldehyde and the numerous', amines and amides describedhereinbefore.

What is garments; v I The process whi hfcoinprises heating to et erequiniolar proportions fa secofi lfyhexityl iaminefjformaldehyde 'and'aI onocal'rhpxylic fattyga'cid amide irrihe presence of amutualsolventand supsequentl tec'oveitng the resultant eond nsan'on iroau'ctifrdm'ihesolvent.

2. Tneprocess 'of'elaim lj'wherein thesaid'amine; is

N -methyl glucamine and, the said amide islauric amide. 1

, IThe processof claim] I'whereintheQ said amine. is

N -methyl glucamine arid'the saidamideisstearica e.

d 'iiionocarhoxylicf fatty acid. do rea Sfiid wherein the nitrogen fofQasecondary.hexityl atfiinojr is linked through methylene'to the nitro enatoin'of' amide.

. 5. An Nfsu'bstituted 'rnonocarboxylic'ffaft through methylene 'to'"the nitrogen atom of said de.

.. ,Nrm t y ,N- n dp me hy li am iie- 7. N-methyl, N-stearamido'niethylg'lucamirie. eheat-es Cit ed n hem orms patent I II UNITEDSTATES PATENTS I 2,216,617 Katz u TOct.1, 1 940 2,3 171,1s1 ,lDfAlelio s Apr. 20,;1943 2,573,489. Rheiner et al Got -30,11 951 2,653,932 Schwartz Sept.29, 1953 (Filed Oct. 20, 1949) I OTI-I ER REFERENCES Degering:An-Outline 'of Organic Nitrogentcompounds, published: by UniversityLithoprinter (Ypsilanti, Michigan) 1953 (pages216 to 217 relied on).

1. THE PROCESS WHICH COMPRISES HEATING TOGETHER EQUIMOLAR PROPORTIONS OFA SECONDARY HEXITYL AMINE, FORM ALDEHYDE AND A MONOCARBOXYLIC FATTY ACIDAMIDE IN THE PRESENCE OF A MUTUAL SOLVENT AND SUBSEQUENTLY RECOVERINGTHE RESULTANT CONDENSATION PRODUCT FROM THE SOLVENT.
 4. AN N-SUBSTITUTEDMONOCARBOXYLIC FATTY ACID AMIDE WHEREIN THE NITROGEN OF A SECONDARYHEXITYL AMINO RADICAL IS LINKED THROUGH METHYLENE TO THE NITROGEN ATOMOF SAID AMIDE.